Chlorinated methyl siloxanes



Patented Sept. 12, 1950 s ZIOFFYICE 1 oHLoRINArEDj un rny'Il SILCWES; Rob Roy McGregor, Verona, and Earl Leathenl nWarrick, Pittsburgh, Pa., assignors to Corning H Glass Works,,Corning-, N. Y., a corporation of New York No Drawing. Original application February 13.

1946, Serial N0.-647,395. Divided and this application March 22, 1950, SerialNo. 151,310

Thisinventidn' relates t new compositions of matterfand methods of preparing them.

This application is a division of the applicants: copending application Serial No. 647,395, filed,

February 13, 1946 which was oopending with and is a continuation-in-part of their U. ,8. Patent No. 2,435,148, filed May 25, 1945 and issued J anuary 2 7 .1948. Patent 2,435,148 was copending with and was acontinuation-in-part of; their Patent No. 2,384,384, filed February 26, 1942 and issued SeptemberQ, 1945 The above application and patents were all assigned tothe assignee of as intermediates in the preparation of othermaterials or which are useful in their own right as coating compositions (as will be later described).

The; chlorination is preferably carried ;out by passing chlorinethrough the methyl siloxaneat a temperaturewithin therange of about C. to 200 C. and preferably in the presence of sunlight. If the siloxane is a liquid, the chlorine may: be passeddirectly through theliquid or through a solution thereof in an inert solvent; if the siloxane is a solid, then it should be dissolved in an inert solvent or heated above its melting point. As a result of such treatment the viscosity of the siloxane increases and if continued for a sufficient time a waxy solid is produced. As high as 65% by weight of chlorine can be introduced in this manner. If the chlorination is stopped at some intermediate point, a viscous liquid is obtained which, upon being heated, increases rapidly in viscosity until ultimately a gel is produced rather than a waxy solid. The melting point of the waxy solid pro- I whether [in a low or? high degreeof chlorination are useful as intermediates in the preparation of other compositions. For example, the chlorinated cyclics having from'one to two chlorine atoms-per cyclic unit are {useful in the preparationofthermally stable liquids of low pour points asv is described in. the above mentioned applications. However,,we have found thepolychlori-. hated products to be particularly useful in-theirown right ascoating materials for glass threads. Thelatter are. composed, of a large number of finaatte uated glass fibers, some of which break during sewing; operations causing fuzzing of the thread and seriously hindering the rapid. and effective fabrication of textile fabrics and the like. When the thread is coated with a polychloriduced by extended chlorination depends upon terminal groups are hydroxyl, chlorine, or trimethyl silicon units, or combinations thereof.

The chlorinated products of our invention natedmethyl siloxane and baked to. a tack-free state, notonly is th fuzzing problem completely solved, but also the tensile strength of the thread is.considerably-increased; The products of the present-invention are also useful as additives to lubricants such as. petroleum oils to improve their resistance to extreme, pressure: The pure, compounds are usefulv as dielectric fluids and are". particularly effective as solvents ,for organic compositions in general. I i

For. a better understanding of our invention reference should be had to the following examples which aregiven by wayof illustration and not limitation. l 1

Example 1 The cyclic pentamer of dimethyl silicone was chlorinated by passing chlorine gas through it at room temperature in the sunlight until analysis showed that it contained about .1 chlorine atom per carbon atom or one chlorine atom per cyclic unit. When the chlorinated product was distilled only about 20% of it boiled in the neighborhood of the boiling point of the pentamer. The remaining was not only higher boiling but was also much more viscous. Continued heating of the latter portion resulted in gelation.

E LEG-7721116 2 The cyclic pentamer of dimethyl silicone was chlorinated by passing chlorine gas through it at room temperature and in the sunlight until analysis showed that it contained about 1.09 chlorine atoms per carbon atom or about 10 chlorine atoms per cyclic unit. The product was a clear waxy solid with a melting point of about 150 C. When heated in an open-beaker without acatalyst for about 15 hours at about C. HCl was evolved and the material lost its waxy had a melting point of 98 C. When the chlorine content was 1.04 chlorines per carbonatom. the '10 melting poin was 165 C. and whenit was 1.20, the melting point was 185 c; 1

Examples A V As in Example 2, the cyclic tetramer of dimethyl silicone was chlorinated at roon te n and then baked to dryness.

4 the same temperature for many hours left the tape essentially unchanged.

Example 6 ,Liquid dimethyl silicone having aviscosity of 590:. centistokes was chlorinated in thesmanner of Example 5 to 9.4% chlorine content. The

.x product was dissolved in G014 to make a 5% solution. Glass thread was dipped into the solution It was found that the; strength of the thread had increased; its grist. andzstiffness had changed only slightly. On

-being subjected; to sewing operations there were perature until analysis showed ittocontain abqut .37 chlorine atoms per carbon atom-or: about 3 chlorine atoms per cyclic unit. When the ch:

rinated material was heated to 250 C., "it formed" a semi-solid mass. From this product an oily liquid was extractedwithbenzene which, on heating overnight at 2-3D- C. became solid.

Example 4 A mixture oi chain polymers of dimethyl silicone was chlorinated until its chlorine content was about 6% by weight and itsviscosity about 75.900 centistokes. The product was heated at 230 Q with 3.7% by weight of boric oxide until a rancher-y solid was obtained: The latter possessed=considerable elasticity without the prop-' erty of -cold flow which is common to most dimethyl silicone polymers treated in like manner with b oric oxide.

Example 5 gel: the. solventvolatilized: The impregnatedtapewasthen-htaatsd; at 250 C. until. the coating became tack-free and hard. Furtherheating at no breaks or fuzzing whereas the untreated thread when subjected to the same test broke twice. and-Was very; fuzzy throughout the entire operation. I

That which is claimed is:

1. A cyclic chlorinated dimethylsiloxane having from 1 to 10 chlorine atoms per cyclic unit.

"2. cyclic chlorinated dimethylsiloxanehaving from 3 lie- 5 silicon atoms persiloxane molecule, andfrom Ito-IQ-chIcrineatoms per cyclic unit! 3-. A cyclic dimethylsi-loxane having from 3 to 5 silicon-atomsper molecule, and from} to 3 chlorine atomsper eyclicunit:

4: A- cyclic chlorinated dimethylsiloxane having lchlorine atom percyclicunit;

' 5. A cyclic chlc irina-teozl dimethylsiloxane having from 3- to 5=silicon atoms per siloxa-ne molecule; and l chlorine atom per cyclic unit.

6. A chlorinated cyclic I pentamer ofdimethylsiloxan'e having 1- chlorine atomper cyclic unit.

FADE-ROY MCGREGORJ EARL LEATHEN" WARR'ICK.

"REFERENCES CITED The following relerencesare of recordln the. filejof; this patent:'

. UN IEDt ATE t f NTS Number- "OTHER, REFERENCES .Krlel91e.=et.al., Jour; Chem. Sou," vol. 68 (1.9460. 

1. A CYCLIC CHLORINATED DIMETHYLSILOXANE HAVING FROM 1 TO 10 CHLORINE ATOMS PER CYCLIC UNIT. 